Disazo- and polyazo-quinolinedyestuffs



Patented Apr. 27, 1954 UNITED STATES PATENT OFFICE DISAZO- AND POLYAZO-QUINOLINE- DYESTUFFS No Drawing.- Application June 22, 1951, Serial No. 233,122

Claims priority, application Switzerland June 28, 1950 9 Claims. (01. 260-155) 1 According to this invention valuable disazoand polyazo-dyestufis are made by coupling a diazo compound of an amine of the formula in which R1 represents an S-hydroxyquinoline radical bound in the 5-position to the azo group, with a 1-hydroxynaphthalene-3-sulfonic acid which contains in the ,B-position of the 6-membered ring of the naphthalene nucleus not containing the hydroxyl and sulfonic acid groups an amino group, preferably a substituted amino group.

The diazo components of the above formula can be made by coupling diazotized 5-amino-2- nitrobenzene-l-carboxylic acid or 5-amino-2- acylaminobenzene-l-carboxylic acid with an 8- hydroxyquinoline capable of coupling in the 5- position, and reducing in the resulting monoazodyestuii the nitro-group to an amino group or hydrolyzing the acylamino group. As 8-hydroxyquinolines capable of coupling in the 5-position, there come into consideration, for example, 8- hydroxyquinoline-7-sulfonic acid and above all 8-hydroxyquinoline itself. The coupling is advantageously conducted. in an alkaline medium, for example, a medium rendered alkaline with ammonia. The reduction of the nitro group to an amino group is carried out under conditions such that the azo group is not attacked, for example, in an alkaline medium by means of an alkali metal sulfide or an ammonium sulfide at a moderately raised temperature. The hydrolysis of the acyl amino group is advantageously carried out by heating the product in a dilute solution of an alkali metal hydroxide.

As coupling components there are used in the present process l-hydroxynaphthalene-B-sulfonic acids which contain in the 6-membered ring of the naphthalene nucleus not containing the hydroxyl and sulfonic acid groups in a fi-position, thus in the 6- or I -position, an amino group. As examples there may be mentioned 1-hydroxy-7- aminonaphthalene-3-sulfonic acid (more usually named 2 amino 8 hydroxynaphthalene 6- sulfonic acid) and especially l-hydroxy-G-aminonaphthalene-3-sulfonic acid (more usually named 2 amino 5 hydroxynaphthalene 7 sulfonic acid), and advantageously substitution products thereof.

When the coupling is carried out with 2-amino- 5-hydroxynaphthalene-7-sulfonic acid itself the coupling may be carried out in an acid or alkaline medium, the diazo compound, as is known, entering the l-position of the azo component in the case of acid Coupling and the 6-position in the case of alkaline coupling. When the coupling occurs in the 1-position valuable intermediate dyestuffs are obtained, which may with advantage be converted into polyazo-dyestuiis by coupling them in an alkaline medium with a further diazo compound, such, for example, as a diazotized 4- amino 4' hydroxy 1:1 azobenzene 3- carboxylic acid (which may, if desired, contain further substituents) In the case of the disazo dyestuiis, which are formed by'coupling diazo compounds of the aforesaid constitution with 2-amino-5-hydroxynaphthalene-7-sulfonic acid in an alkaline medium, it is of advantage to carry out further reactions at the NH2 group, for example, by further diazotizing these compounds and coupling them with suitable azo components or by reacting them with acylating agents such, for example, as acid halides, with phosgene or with heterocyclic compounds containing reactive halogen atoms such as cyanuric chloride or dichloroquinazoline. When reactions are carried out with the latter compounds containing more than one reactive halogen atom, these compounds can advanta-- geously be used to serve for the condensation of the resulting disazo-dyestuiis with further aminoazo dyestuffs of the same or a different kind to form polyazo-dyestuifs.

Very valuable polyazo dyestufis are obtainedby coupling diazo compounds of the foregoing constitution in an alkaline medium with substi tution products of 2-amino-5-hydroxynaphthalene-l-sulfonic acid. As substitution products there come into consideration, for example, azo

dyestuffs which have been obtained by coupling the aforesaid acid with a diazo compound in an acid medium. Especially valuable are the disazoand polyazo dyestuffs obtainable by the present process from N-substitution products of Z-amino- S-hydroxynaphthalene sulfonic acid. Such N- substitution products may be, for example, 2-

arylamino 5 hydroxynaphthalene 7 sulfonic acids or 2-acylamino-5hydroxynaphthalene-7- sulfonic acids. In this connection there may also be used compounds capable of coupling twice such, for example, as 5:5- dihydroxy-2:2'-dinaphthylamine-7 7disulfonic acid, 5 5-dihydroxy-2 2-dinaphthylurea-'Z 7'-disulfonic acid or compounds obtainable by condensing two molecular proportions of 2 amino-S-hydroxynaphthalene-7-sulfonic acid with one molecular proportion of cyanuric chloride. Such azo components capable of coupling twice may be coupled on one side or on both sides with diazo compounds of the foregoing constitution. If desired, the cou-, pling may be carried out on one side with a diazo compound of that kind and one the other side with any desired diazo compound, for example with a diazo-compound of an amino monoazo dyestuff of the formula wherein R4 stands for a benzene radical containing the azo group in para-position to the amino group and containing in ortho-position to the amino group a substituent capable of taking part in the formation of metal complexes such as a lower alkoxy, for example, a methoxy group or a carboxylic acid, and R5 stands for a radical of a l-hydroxybenzene-Z-carboxylic acid bound to the azo group in its 4-position or an S-hydroxyquinoline bound to the azo group in its 5-position.

For this purpose the following compounds may be used: 2 methyl 4 amino 5 methoxy- 4 hydroxy 1:1 azobenzene 3 carboxylic acid,.4 amino 4 hydroxy 1:1 azobenzene 3,3 dicarboxylic acid.

Valuable dyestuffs can also be obtained by coupling diazo compounds of the foregoing constitution with N-substitution products of 2- amino 8 hydroxynaphthalene 6 sulphonic acid, among which there may be mentioned as examples thefollowing N-substitution products: 2 phenylamino 8 hydroxynaphthalene 6- sulfonic acid, Z-benzoylamino-8-hydroxynaphthalene-6-sulfonic acid, and 8 8'-dihydroxy-2 :2- dinaphthylamine-G 6' -disulfonic acid.

The compounds of the formula are advantageously diazotized by the so-called indirect method, for example, by mixing an aqueous weakly alkaline solution of an alkali salt of the compound in question, which contains the necessary quantity of nitrite, with an excess of hydrochloric acid.

The latter diazo compounds may be coupled with 2-amino-5-hydroxynaphthalene-7-sulfonic acid or a substitution product thereof or with N- substitution products of 2-amino-8-hydroxynaphthalene-G-sulfonic acid by the customary known methods for coupling with such azo components.

The new disazoand polyazo-dyestuffs obtainable by the present process correspond to the general formula OOOH in which R1 represents an 8-hydroxyquinoline radical bound in the 5-position to the azo group and R2 represents the radical of a l-hydroxynaphthalene-3-sulfonic acid which contains in a B-position of the 6-membered ring of the naphthalene nucleus not containing the hydroxyl and 4 sulfonic acid groups an amino group, preferably a substituted amino group.

These dyestuffs are suitable for dyeing a very wide variety of materials, for example, animal fibers such as wool, silk and leather. The dyestuffs obtainable from 2-amino-5-hydroxynaphthalene-'l-sulfonic acid or substitution products thereof are very well suited for dyeing and printing cellulose materials such as cotton, linen and artificial silk and stable fibers of regenerated cel lulose. The dyestuffs may with advantage be treated on the fiber or partially on the fiber and partially in the dyebath with agents yielding metal by known methods. It is of advantage, for example, to use the process of U. S. Patent No. 2,148,659. in which first the dyeing and then the treatment with an agent yielding metal are carried out in the same bath. In this connection there come into. consideration as agents yielding metal preferably those which are stable towards alkaline solutions, such as complex copper tartrates and the like.

In some cases especially valuable dyeings can be obtained by working according to the process in which a dyeing or printing produced with the metal-free dyestuff is after-treated with an aqueous solution containing a basic condensation product of formaldehyde with a compound which contains at least once the atomic groupfor example, dicyandiamide or dicyandiamidine, or which 'can easily be converted into such a compound, for example, cyanamide, and which solution also contains a Water-soluble copper compound, and especially a water-soluble complex copper compound. Such a process is described, for example, in British Patent No. 619,969.

The following examples illustrate the invention, the parts and percentages being by weight:

Example 1 A moist paste corresponding to 30.8 parts of the aminoazo-dyestuif of the formula the formula HOaS- COOH HO is completely precipitated with sodium chloride. coupling 2 acetylamino-5-aminobenzene-l-car- It is separated by filtration and dried. It is obboxylic acid in an alkaline medium with 8-hyd in the m f a r p r Which is droxyquinoline, and then splitting ofi" the acetyl soluble in water with a reddish blue coloration grgup by prolonged heating of t dyestufi 1 and dyes fibers of natural cellulose and fibers of tion with sodium hydroxide solution of 5 per cent regenerated cellulose from a bath containing Strength sodium sulfate violet tints which change to reddish blue dyeings of very good fastness to light and washing when treated with a copper salt.

Instead of 2-phenylamino-5-hydroxynaphthal0 lene-7-sulfonic acid there may be used parts of 2-(4'-methoxy) -phenylamino 5 hydroxy- Example 2 23.9 parts of 2-amino-5-hydroxynaphthalene- 7-sulfonic acid in the form of a freshly precipitated suspension are coupled in a medium na hthal n q ulfoni acid The d estufi so rendered weakly acid with acetic acid with the obtained corresponds to the formula diazo compound obtained as described in EX- I COOH 11( ample 1 from 30.8 parts of the aminoazo dyestuff and yields in the presence of a copper salt a of the formula brighter reddish blue dyeing.

By using instead of 2-phenylamino-5-hydroxynaphthalene 7 sulfonic acid the isomeric 25 2-phenylamino-8-hydroxynaphthalene 6 sul- 00011 ionic acid, there is obtained a dyestuif which corresponds to the formula Coupling comes to an end after several hours,

and then a sufficient quantity of sodium carbonate is added to produce an alkaline reaction, and the dystuff is precipitated by the addition of sodium chloride and separated by filtration. The disazo dyestuff is redissolved in warm water and HO- N=NQN=N N/ COOH HO and dyes cellulose fibers by the single bath or 2-bath after-coppering process grey-blue tints.

By using instead of 2-phenylamino-5-hydroxynaphthalene-'l-sulfonic acid an equivalent quantity of 2- (4-acetylaminobenzoyl) -amino-5-hydroxynaphthalene-7-sulfonic acid, there is obthe solution is cooled with ice to 4 C. tained a dyestufi which corresponds to the for- 30.1 parts of the monoazo dyestufi, obtained mula by coupling the diazo compound from 15.3 parts Hois- NHOOC NHCOCH;

of 4-amino-1-hydroxybenzene-2-carboxylic acid in an acid medium with 13.7 parts of l-amino- The amino-monoazo-dyestufi used as start- 2-methoxy-5-methylbenzene, are diazotized in ing material in this example may be preknown manner and then coupled with the alkapared as follows: 18.2 parts of 5-amino-2-nitroline solution of the disazo dyestufi obtained as benzene-l-carboxylic acid are dissolved with 5.5 described above. After 6 hours the whole is parts of anhydrous sodium carbonate in 200 parts heated to 70 0., the tetrakisazo dyestufi is of water, and the Whole is acidified with 35 parts completely precipitated by means of sodium chloof hydrochloric acid of 30 per cent. strength and ride, separated by filtration and dried. There is diazotized in known manner with 7 parts of so- 60 obtained a dark powder which dissolves. in water dium nitrite. The diazo compound is run into with a blue coloration and dyes fibers of natural an ice-cold solution of 14.5 parts of S-hydroxycellulose and fibers of regenerated cellulose from quinoline. 30 p rts of amm ia solution f 25 p r a bath containing sodium sulfate navy blue tints cent. strength and 200 parts of water. Dyestufi which when after-treated with a nickel or copper formation occurs immediately, and after 2 hours alt, in th ame r a fresh bath yield dyeings the reduction of the nitro group is commenced hi r fast t light and washing. by heating the whole up to 4550 0., adding in Example 3 portions a solution of 38 parts of crystalline sodium sulfide in 100 parts of water, and stirring The diazo compound obtained as described in for 1 /22 hours. When no more sodium sulfide is Example 1 from 30.8 parts of the aminoazo dyetaken up, the aminoazo-dyestuif is precipitated stuff described therein is coupled in the presence by the addition of sodium chloride, separated by of sodium bicarbonate at 0-4? C. with 46.1 parts filtration and the moist paste so obtained is adof 5:5-dihydroxy-2:2-dinaphthylamine-7 :7'-divantageously used for the further synthesis.

The same aminoazo dyestufl can be obtained by bonate are then added, and there is added the and yields on cellulose fibers when after-coppered blackish-blue dyeings.

sulfonic acid. 15 parts of anhydrous sodium caris completely precipitated by means of sodium chloride, separated by filtration and dried. It is a dark powder which dissolves in water with a blue coloration and dyes fibers of natural cellulose and fibers of regenerated cellulose reddish lue tints which when after-treated with a copper 2U salt change to blue dyeings which are fast to light and washing.

A similar tetrakisazo-dyestuff which corresponds to the formula N C O O 11 EC is obtained by coupling the diazo compound of 61.6 parts of the aminoazo dyestulf described in Example 1 with 46.1 parts of 5 5'-dihydroXy-2 :2- dinaphthyl-amine-T:7-disulfonic acid in the presence of 35 parts of anhydrous sodium carbohate.

By using in the procedure described in the last paragraph, instead of 5:5'-dihydroxy-2:2-dinaphthylamine-7:7-disulfonic acid, an equivalent quantity of 5:5-dihydroXy-2:2-dinaphthyl urea-7 :7-disu1fonic acid with the diazo compound from 61.8 parts of the aforesaid amino monoazo dyestuff, there is obtained a. tetrakisazo dyestuff which dyes cellulose fibers violet-grey tints when after-coppered by the single bath or 2-bath process.

From 61.6 parts of the diazotized aminoazo dyestuif according to Example 1 and 46.1 parts of 8:8 dihydroxy 2:2 dinaphthylamine 6:6-

disulfonic acid there is obtained a tetrakisazo dyestuif which also dyes cotton violet-grey tints by the single bath or 2-bath after-coppering process.

| N IOOH HO Example 4 100 parts of cotton are entered at 50 G. into a dyebath consisting of 400 parts of water, 2 parts of anhydrous sodium carbonate and 2 parts of the dyestufi obtainable .as described in the first paragraph of Example 1. The temperature is raised to 90-95 C. in the course of minutes, parts of crystalline sodium sulfate are added,

8. C. The whole is then allowed to cool to about 70 (3., and the cotton so dyed a blue-violet tint is after-treated in the manner described in any one of the following paragraphs:

(a) The dyeing is rinsed in cold water and treated for /2 hour at C. in a bath containing 4000 parts of water, 3 parts of crystalline copper sulfate and 1 part of acetic acid. The material is then rinsed and dried. A reddish blue dyeing of good fastness to light and having very good properties of wet fastness is obtained.

(12) To the dyebath, which has been cooled to about C., are added 4 parts of complex copper sodium tartrate of approximately neutral reaction, coppering is carried on for /2 hour at about C. and the dyeing is rinsed with cold water. If desired the. dyeing may be soaped by after-treatment for /2 hour in a bath containing, per liter of water, 5 grams of Marseilles soap and 2 grams of anhydrous sodium carbonate. A reddish blue dyeing is obtained of good fastness to light and having good properties of wet fast-- ness.

(0) The dyeing is rinsed with cold water and then after-treated for /2 hour at 20 C. in a solution prepared by dissolving 4.5 parts of a watersoluble condensation product of dicyandiamidine and formaldehyde, 1.5 parts of copper acetate and 6 parts of a concentrated aqueous solution of am in 3909 Darts of water, and adding 2 parts of anhydrous sodium carbonate to the solution containing cupric tetramine acetate. The material is then rinsed and dried. A reddish blue dyeing is obtained which is distinguished by good fastness to light and very good properties of wet fastness.

What is claimed is:

1. An azo dyestuff which corresponds to the formula in which the NH-groups are bound in c-position to thenaphthalene nuclei, is, m and at each represents a whole number of at the most 2, R3 stands for a benzene radical, R1 stands for a benzene radical containing the azo groups in para-posi tion to one another and containing in orthoposition to: the azo group connecting R4 with the naphthalene nucleus a substituent selected from the group consisting of a methoxy group and a and dyeing is carried on for 30 minutes at -400 75 carboxylic acid group, and R5 stands for a memher selected from the group consisting of a radical of a 1-hydroxybenzene-2-carboxylic acid 4. An azo dyestuff which corresponds to the formula COOH OH bound to the azo group in 4-position and the m in whichwrepresentsamember of the group conradical of the formula 2. An azo dyestufi which corresponds to the COOH HO HO N=N in which R3 represents a benzene radical and the radical NHR3 is bound to the nap th ene nucleus in a fi-position.

3. An azo dyestufi' which corresponds to the formula sisting of the radicals -NI-I and -NIICOI-IN- R4 stands for a benzene radical containing the 5 azo groups in para-position to one another and containing in ortho-position to the azo grou-p connecting R4 with the naphthalene nucleus a substituent selected from the group consisting of a methoxy group and a carboxylic acid group, and R5 stands for a member selected from the group consisting of a radical of a l-hydroxybenzene-Z-carboxylic acid bound to the azo group in Jr-position and the radical of the formula 5. The azo dyestuif which corresponds to the HOaS- COOH HO COOH HO 6. The azo dyestufi which corresponds to the in which R3 represents a benzene radical. formula H038 NHC OCH| HO N=N N=N N/ 0 0 OH HO COOH 7. The azo dyestufi which corresponds to the formula 0 OH HO 8. The azo dyestufif which corresponds to the formula 9. The azo dyestufi which corresponds to the formula Hols NH SOaH HOpN= QN=N N=N-Q N=N on 00H H on H000 N m cm, 

6. THE AZO DYESTUFF WHICH CORRESPONDS TO THE FORMULA 